Water-insoluble disperse monoazo dyes

ABSTRACT

WATER-INSOLUBLE DISPERSE MONOAZO DYES HAVING AN AROMATIC OR HETEROCYCLIC DIAZO COMPONENT AND A PARA-AMINOPHENYL COUPLING COMPONENT IN WHICH THE AMINO NITROGEN ATOM IS SUBSTITUTED BY PHENYLETHYL AND BY AN ETHYL OR PROPYL GROUP SUBSTITUTED BY HYDROXY, METHOXY, ETHOXY, ACETOXY O PROPIONYLOXY GROUPS. THESE DISPERSION DYES ARE USEFUL AS APPLIED TO HYDROPHOBIC FIBERS, ESPECIALLY POLYESTER FIBERS SUCH AS POLYETHYLENE TEREPHTHALATE AND EXHIBIT GOOD FASTNESS TO LIGHT, WETTING AND THE EFFECT OF HIGH TEMPERATURES.

lJ'nitedStates Patent WATER-INSOLUBLE DKSPERSE MUNQAZU DYES Erwin Hahn, Viernheim, and Hans Guenter Wippel,

Ludwigshafen (Rhine), Germany, assignors to lladische Anilin- 8: Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Sept. 16, 1968, Ser. No. 762,317

Claims priority, application Germany, Sept. 20, 1967,

P 16 44 069.4] lint. Cl. C09}; 29/00, 29/08; D061) 1/04 US. Cl. 260-158 2 Claims ABSTRACT OF THE DllSCLOSURE This invention relates to water-insoluble monoazo dyes having the general Formula I:

in which D denotes the radical of an aromatic or heterocyclic diazo component, X denotes a hydrogen atom or a loW molecular Weight alkyl or alkoxy group, Y denotes a hydrogen, chlorine or bromine atom or a low molecular alkyl, alkoxy or acylamino group, R denotes an unsubstituted or substituted phenyl radical, R denotes a hydroxyalkyl, acyloxyalkyl or alkoxyalkyl radical and n denotes one of the integers 1 and 2.

In addition to the specific substituents for X and Y already mentioned, the following are further examples: methyl, ethyl, methoxy or ethoxy for X and methyl, methoxy, acetylamino or propionylamino for Y.

Examples of substituents for the phenyl radical R are chlorine atoms or bromine atoms or alkyl groups having one to four carbon atoms or alkoxy groups having one or two carbon atoms.

The radicals R may contain one or more hydroxy, alkoxy or acyloxy groups and the groups may be combined together.

Dyes which are particularly valuable industrially have the following general formula:

in which D denotes the radical of an aniline derivative bearing halogen atoms or nitro, alkylsulfonyl, cyano, carboxylic ester, alkoxy, trifiuoromethyl, alkyl or acylamino groups as su'bstituents or the radical of a thiazole, thiadiazole or benzothiazole, X denotes a hydrogen atom or a methoxy or ethoxy group, Y denotes a hydrogen, chlorine or bromine atom or a methyl, ethyl, acetylamino or propionylamino group, R denotes a ,B-hydroxyethyl, fl-hydroxypropyl, on dihydroxypropyl, B hydroxylchloropropyl, ,8 methoxyethyl, [3 ethoxyethyl, ,3 hydroxy 'y methoxypropyl, fi-acetoxyethyl, ,6 pro'pionyl- 3,542,767 Patented Feb. 15, 1972 oxyethyl, ,8 acetoxypropyl or 18, diacetoxypropyl group and n denotes one of the integers 1 and 2.

Dyes according to the invention are eminently suitable, particularly in finely divided form, for dyeing textile material of acetylcellulose such as secondary cellulose acetate or cellulose triacetate, polyamides such as nylon 6 or nylon 6.6 and particularly linear polyester such as polyethylene glycol terephthalate. The dyeings obtained are distinguished by good wet and light fastness and also very good resistance to high temperatures.

The carrier method and preferably the HT-method are suitable as dyeing methods.

The new dyes are obtained for example by reacting a diazo compound of an amine having the general Formula II:

D-NH with a coupling component having the general Formula (III) 1-amino-4-methylbenzene, 1-amino-4-chlorobenzene, 1-amino-4-bromobenzene, l-amino-4nitrobenzene, 1-amino-2-cyano-4-nitrobenzene, 1-amino-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene, 1-amino-4-carbomethoxybenzene, 1-amino-2-carbomethoxy-4-nitro-6-chlorobenzene, 1-amino-2-carbomethoxy-4-nitro-6-bromobenzene, 1-amino-2 bromo-4-carbomethoxybenzene, 1-amino-2-trifiuoromethyl-4-nitrobenzene, 1-amino-2-rnethyl-4-nitrobenzene, 1-amino-2,4-dichlorobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-2,6-dibromo-4-methylsufonylbenzene, 1amino-2,6-dichloro-4-nitrobenzene, 1-amino-2,4-dinitro-6=bromobenzene, 1-amino-4-acetylaminobenzene, 1 amino-2,4-dinitro-6-chlorobenzene, 1-amino-2,4-dinitrobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-Z,6-dibromo-4-nitrobenzene, 1-amino-2,4-bis- (methylsulfonyl) -b enzene, 1-amino-4-cyano-Z-methylsulfonylbenzene, 1-amino-2-methylsulfonyl-4-nitrobenzene, 1-amino-2-methylsulfonyl-4-nitro-6-chlorobenzene, 1-amino-Z-methylsulfonyl-4-nitro-6-bromobenzene, 1-amino-2-cyano-4-methylsulfonylbenzene, 1-amino-2,4-dicyanobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-chloro-4-cyanobenzene, l-amino-Z-chloro-4-nitrobenzene, l-amino-2-chloro-4-methylsulfonylbenzene, 1-amino-4-chloro-2-methylsulfonylbenzene, 1-arnino-2-methoxy4-nitrobenzene, and l-amino-2-methoxy-4-nitro-6-bromobenzene.

Examples of diazotisable heterocyclic amines DNH are: 2-aminothiazole, Z-aminobenzothiazole, aminothiadiazoles and their derivatives bearing nonionic groups as substituents, such as 2-amino-5-nitrothiazole,

2-amino-6-methoxybenzothiazole,

2-amino-6-carb omethoxybenzothiazole,

Z-amino-6-methylsulfonylbenzothiazole,

2-amino-6-nitrobenzothiazole,

2-amino-5-phenylthiadiazole- 1,3,4)

3-methylmercapto-S-aminothiadiazole-( 1,2,4)

3- B-carbomethoxyethylmercapto -5-aminothiadiazole- 3- (B-carboethoxyethylmercapto) -5-aminothiadiazole- Examples of coupling components corresponding to the general Formula III are:

and the corresponding anilines bearing methyl or chlorine as substituents in meta-position or N-benzyl-N-B-hydroxyethyl-Il-acetylamino aniline, N-benzyl-N-fl-hydroxyethyl-3-propionylaminoaniline, N-benzyl-N-fl-methoxyethyl-3-acetylaminoaniline, N-benzyl-N-p-acetoxyethyl-3-acetylaminoaniline,

d. N-benzyl-N-fi-hydroxyethyl-3-acetylamino-6- methoxyaniline, N-benzyl-N-fi-hydroxyethyl-3-acetylarnino-6- ethoxyaniline, N-benzyl-N-fl-acetoxyethyl-3-acetylamino-6- methoxyaniline or N-benzyl-N-p- -dihydroxypropyl-3-acetylamin0-6- methoxyaniline.

The invention is illustrated by the following examples. Statements as regards parts and percentages in the following examples relate to Weight.

EXAMPLE 1 A mixture of 13.8 parts of l-amino-4-nitrobenzene, 100 parts of water and 30 parts of concentrated hydrochloric is stirred for one hour while stirring, 200 parts of ice is added and then at 0 to 5 C. a solution of 6.1 parts of sodium nitrite in 20 parts of water is allowed to fiow in. The whole is stirred for an hour, any excess of nitrite present is removed by adding 0.5 part of sulphamic acid and the diazo solution is filtered. The filtrate is added gradually to a solution of 22.7 parts of N-benzyl-N-fihydroxyethylaniline in 500 parts of acetone, 20 parts of concentrated hydrochloric acid and 150 parts of ice. The whole is stirred for another thirty minutes, another 300 parts of ice is added, the reaction mixture is neutralized with a solution of 42 parts of sodium acetate in 200 parts of water and stirred for another sixteen hours. The dye, deposited in crystalline form, is suction filtered, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It has the formula and dyes polyethylene glycol terephthalate bright red shades having good fastness properties.

If the diazo components and coupling components set out in the following table are used instead of the components in Example 1, dyes having similar good properties are obtained. In all the following tables E= Example No. and Shade=shade of the dyeing on polyester.

CHzCsH:

CHz-CqH Yellow orange:

5 EXAMPLE 7 for thirty minutes and the reaction mixture is poured onto 12 parts of 1-amino-4-nitrobenzene-2-methylsulfone is ice. Following stirring for two hours the dye which has introduced at 0 to 5 C. while stirring into a mixture of been deposited in crystalline form is suction filtered, 14.5 parts of nitrosylsulfuric acid having a content of Washed with water until neutral and dried under subatmos- 13.1% of dinitrogentrioxide and 55 parts of 85% sulfuric 5 pheric pressure at 50 C. 111 d l h l glycol acid and the whole is stirred for four hours. A solution ephthalate ruby shades having excellent resistance to high of 11.35 parts of N-benzyl-N-B-hydroxyethylaniline and temperatures. 50 parts of glacial acetic acid is allowed to flow gradually Similar dyes are obtained with the components given into the diazo solution at 0 to 5 C., the whole is stirred in the following table:

E Diazo component Coupling component Shade 8 (3N C2H4CQH5 Ruby.

-N o N---- Nl'1 fl Q CH2-CHCTI OH 9 .1 (IN C 21140 5H5 Claret.

--N OzN- NH1 l CHzCHzOH 01 l 131 CH 10 $020115 CzH4CgH D0.

OgN-- NHg I CH2CH-CH2OH I CH: 01 H 11 .1 1'31 C 2H4 C 4H Yellow brown;

C O zN- -NH2 l C 2114 O H l Cl Br 12 ITTO: CzHaCaHs Violet.

Q- O N- NH:

l CzHrOH CH3 Br 13.. 1 (ll C H4C H Yellow brown.

OzN- -NH:

I C2114 O C- C H3 Cl ll Br 14. (IJOzCHa CzH4CnH5 Red brown.

O N --NH2 l C 2H4 O C- 0 H3 CH3 ll Br 15.. 0 Br CZHACuHg Orange red.

H C H O-C- NHz l CZIIAOH Cl 16 S OeCHs 011140 11 Violet blue.

OzN- NH l C 2H4 O H l 3 N0 17 $020133 C HzCnH Red brown.

O2N' NHz I CHz-CH-OlhOII Br H 18 "1.... Br CHQCQHE Orange.

0 l 11 C ll;O-C--- *NH:

- l C 2H4O CH Br l9.....,... OCHa /C2H;0ll Ruby.

021v \NH2 l C H C sH HNCOCH;

7 EXAMPLE 20 50 parts of a mixture of anhydrous acetic acid and propionic acid in the ratio 17:3 is allowed to flow at to C. into a mixture of 14.5 parts of nitrosylsulfuric acid having a content of 13.1% of dinitrogen trioxide and 15 parts of concentrated sulfuric acid and then 7.25 parts of 2-amino-5-nitro-l,3-thiazole is added to this mixture at 0 to 5 C. Another 50 parts of the said mixture of acetic acid and propionic acid is added and, after the whole has been stirred for three hours, 2 parts of urea is added at 0 to 5 C. The clear solution obtained is allowed to flow gradually at 0 to 5 C. into a solution of 11.35 parts of N-benzyl-N-B-hydroxyethylaniline in 250 parts of acetone, parts of concentrated hydrochloric acid and 75 parts of ice, the whole is stirred for thirty minutes, 100 parts of ice-water is added and stirring is continued for another sixteen hours. The dye which has been deposited in crystalline form is suction filtered, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It dyes polyethylene glycol terephthalate cloth blue violet shades having very good thermal fastness properties.

EXAMPLE 21 50 parts of phosphoric acid is allowed to flow at 0 to 5 C. into a mixture of 14.5 parts of nitrosylsulfuric acid having a content of 13.1% of dinitrogen trioxide and parts of concentrated sulfuric acid. Then 8.85 parts of 2-amino-5-phenyl-1,3,4-thiadiazole is added to the mixture. Three hours later 2 parts of urea is added at 0 to 5 C. while stirring. The resultant diazo solution is allowed to flow gradually at 0 to 5 C. into a solution of 14.2 parts of N-benzyl-N-fi-hydroxyethyl 3 acetylaminoaniline in 250 parts of acetone, 10 parts of concentrated hydrochloric acid and 75 parts of ice. After the whole has been stirred for thirty minutes, 1000 parts of ice-water is added and stirring is continued for sixteen hours. The dye which is deposited in crystalline form is suction filtered, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It has the formula I HNCO CH CHFCGH5 CHQCHZOH and dyes polyethylene glycol terephthalate fibers red shades having excellent thermal fastness properties.

EXAMPLE 22 acid and propionic acid are added followed, after the whole has been stirred for three hours at 0 to 5 C., by 2 parts of urea. The reaction mixture obtained is allowed to flow gradually at 0 to 5 C. into a solution of 13.8 parts of N-fi-phenylethyl-N-fl-hydroxyethyl-3-chloroaniline in 250 parts of acetone, 10 parts of concentrated hydrochloric acid and 75 parts of ice. Thirty minutes later 1000 parts of ice-water is added and the Whole is stirred for another sixteen hours. The dye is suction filtered, Washed with water until neutral and dried at 50 C. at subatmospheric pressure. It has the formula 1 onzerrgonn EXAMPLE 23 parts of a mixture of anhydrous acetic acid and propionic acid in the ratio of 17:3 is allowed to flow at 0 to 5 C. into a mixture of 18.5 parts of nitrosylsulfuric acid having a content of 12.9% of dinitrogen trioxide and 20 parts of concentrated sulfuric acid and then there is added to this mixture at 0 to 5 C. 13.75 parts of 2- amino-6-carboethoxybenzothiazole. Another 60 parts of the said mixture of acetic acid and propionic acid is then added, the whole is stirred for another four hours at 0 to 5 C. and then 2 parts of urea is added. The diazo solution obtained is then allowed to flow gradually into a solution of 14.6 parts of Z-methoxy-S-acetylamino-N-B-hydroxyethyl-N-benzylaniline in 250 parts of acetone, 10 parts of concentrated hydrochloric acid and parts of ice, the whole is stirred for thirty minutes and 1000 parts of ice-water is added. The dye which is deposited in crystalline form is suction filtered after stirring for sixteen hours, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It dyes polyethylene glycol terephthalate fibers claret shades.

EXAMPLE 24 The dye having the formula:

which dyes secondary cellulose acetate red brown shades having excellent fastness to light and gas fume fading is obtained by a method analogous to that in Example 7 from 2-carbornethoxy-4-nitro 6 bromoaniline and N- benzyl-N- fl-hydroxyethylaniline.

Dyes which dye polyester in the shades indicated are obtained from the components given in the following table:

TABLE-Continued E Diazo component Coupling component Shade 28- fl) Scarlet.

OzN-NHZ 021140 oom CHz-CaH5 29... Same as above 1 Orange- CHz-CH-CH2OH C 2CaH5 30 do OZILOH Red.

I C 2 1- e s C1 31 .do 0H Scarlet.

CH H-OH2OH I 2 4CnH5 C1 32..- I 01 02114011 Dark red.

O2N NH:

C H2- C H1 33... Same as above CzH40H Do.

I CzHr-CeH; CH3

34 -do E) Red.

C zHaO C 0 H3 Q I 0211 -0011 CH;

35 -(10 021140 H Dark red.

2 4-CsH5 36...--...d0 n Red.

C 2H4 O 0- CH3 37 do C2H4OH Dark red.

; zflr-Oafls C1 38 S OzCHa C2H4OH Red violet;

3 OzN NH I C2H CuH CH3 39-.- Same as above Ruby.

C 21140 (J)- 0 H3 I C2H4-CGH5 CH3 40 do C2H4OH Rose,

41 .do Rod.

O 1% CzH4O -CHa TABLEContinued E Diazo component Coupling component Shade 42..- CN CzH OH Ruby.

O 2N NHz CHg-CBH5 43... Same as above (I) Dark red.

I 0 21h 0 C- C H3 CHZ-CGHE 44 .du 0111 011 Rod violet:

l CgHl- C9115 C 45 ..do Ruby.

C2H4O C-GH; Q

l CzIL-CuH; C 46 ..do 02H 0H Dark red.

C2H4CaH; C1 47 .do H D0.

0 H4 0 CCHa CzH4-C0H;

48 do /C2H OH Ruby.

49... Iir H Yellow brown.

C2 40 C-O O :N- NH: 1 01 CH2-Co a 50... Same as above (3 11 011 Brown red.

I C:H4CO 5 CH;

51 .-do Red brown.-

C2H4O C-CHB l CzH4C5H CH; 52 ..do 0113 0 CH; Yellow brown.

I C2H4-C0H; 53... COzCli; 02114011 Red blOWll.

OzN- NHa I CzHr-CQHE Br 54..- Same as above H Brown red.

0211 0 C-CH;

CHzCuHa 55 ..d0 02114011 Ruby.

CzHr- 00115 1 3 TABLE-Continued 1 4 E Diazo component Coupling component Shade 56-.- (llO CHa 0 Dark red.

2 2 C2H O -CH;

I 31 l 2 4CoH5 57... -N 0 Ha /C2H O H Blue.

O2N[ LNPH S l 2 4 o s 58... Same as above CH3 0 Blue violet.

C H O ('L- 0 H (EH3 C FTP-( H 59-.. do O Violet.

C2H4O CH C Hz-CuH5 60... do OH Blue violet.

C Ha-H-CHzOH C2H4 CflH5 61 do (3211 011 Violet.

(In O2H4C H C 2H4- u s 63 do C Hz-CaHa Blue.

I IlICO CH CZHOH NN C H OH Scarlet.

l S CzH4C0H5 65... Same as above Red.

CzH O )CH;

C Hz-C H 66 do O H Salmon.

CH -PJHCH2OH N CzH -CgH 67 d0 C2H4OH Red.

(IJH CzH C H 68 .do O Scarlet.

C2H O l-CH; Q-

(IJH: Cz ra s 69 do 0 Orange.

C 11 0 (I l-43 H TABLE-C0ntinued E Diazo component Coupling component Shade 70.-- CH OfiC1Hr-fiN /CZH OH Red.

O Hz-CHf,

71... CH;OCC2H S N H Scarlet.

O H OC-CH I 2 z 4 a GzHr-Cdfi 72... Same as above /C2H4OH Red:

I C 211 -05115 C] 73- CH S-"N 0111 011 Dark red:

N J NH 2 s 1 Cz 4- u s 74... Same as above /C,H OH Red:

CHr-Cn b 75 ..do H Scarlet:

0211.0 (l-CH QM CzH|Cu s 76 d0 CzHy-Culi; R056.

CH2ICHCH2OH 77 do C2H|0H Dark red:

I CzH CuH5 CH3 78 ..do H Red! C 2 40 C-C CaHr-co a CH;

79... 0 Dark red.

H CzILOH CflLO-C S NH2 N 0112-06 5 80..- Same as above h) Rod:

021140 CCH5 Q CHg-CgHg 81 ..do (IJH Dark red.

CHzCH-OHzOH C2H4Co s 82.---::;.d0 CzHaQH R058.

C2H4 Ce s 01 3'; do CzHqOH Ruby;

I C2H4 C011 TABLEContinued E Diazo component Coupling component Shade Red. H II C2H5O- S CzH4OC-CH3 CRH-CGH5 CH3 85... Same as above CzH4OH Dark red.

C2H4C8H5 86 do H Red.

C2H4-CsI-L;

87-.. S OzOHg 2CeH5 OzN- NHz Q-N i /CHz-CHOHCH:OH

I CZH4CBH5 01 We claim: in which 1. A monoazo dye having the formula D is a diazotized radical selected from the class con- X sisting of I C2H4 3-methyl-mercapto-5-amino-thiadiazole-(1,2,4), 3-([3-carbomethoxyethylmercapto)-5-aminot thiadiazole-(1,2,4) and Y R 3-( 8-0arboethoxyethylmercapto)-5-aminothiadiazolel2 1n whlch D is a diazotized heterocyclic radical selected from the X is hydrogen or methoxy; Y is hydrogen, chlorine, methyl, acetylamino or propionylamino; and

R is

2-amino-6-methoxy-benzthiazole, Z-amino-6-methylsulfonyl-benzthiazole, Z-amino-6-carbornethoxybenzthiazole,

2-amino-S-phenylthiadiazole-(1,3,4),

3-methyl-rnercapto-iaminothiadiazole-( 1,2,4) 3- B-carbomethoxyethylmercapto -5-aminothiadiazole- 1,2,4) and 3- fi-carboethoxyethylmercapto -5-amino-thiadi- X is hydrogen, methyl or methoxy; Y is hydrogen, chlorine, bromine, methyl, metholiy,

acetylamino or propionylamino; and

p-hydroxy y-methoxypropyl,

B-acetoxyethyl, p-propionyloxyethyl, p-acetoxypropyl or figy-diacetoxypropyl.

fl-hydroxyethyl, fly p py flny yp py fl-hydroxy-' -chloropropyl, ,B-methoxyethyl, B-ethoxyethyl, B-hydroXy-' -methoxypropyl, fi-acetoxyethyl, fi-propionyloxyethyl, fl-acetoxypropyl or B -diacetoxypropyL References Cited UNITED STATES PATENTS 5/ 1938 Krzikalla et al 260-205 7/1941 Dickey et al. 260152 6/1959 Bossard et al 260158 X 7/ 1963 Fishwick et a1. 260207.1 8/1963 Bossard et al 260158 X 5/1964 Suzuki et a1. 260158 12/ 1969 Ramanathan 260158 FLOYD D. HIGEL, Primary Examiner 2. A monoazo dye having the formula US. Cl. X.R.

mg UNITED STATES PATENT OFFMIE CERTIFEATE 0F CGRREUHUN Patent No. 5, ,7 7 Dated February 5, 97

Inventor) Erwin Hahn and Hans Guenter Wippel It is certified that; error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 61, that portion of the formula reading "Y should read Y Column 2, line 7, "6.6" should read 6,6 line 28, "tetents" should read tuents Column 6, in the table, Example 9, under "Coupling component", that portion of the formula reading "fiiH OH" should read Column 8, line 25, "129%" should read 12.8%

Column 15, in the table, Example 71, under "Diazo component", that portion of the formula reaGing CH O-C-CEH, should read CH O-C-C H v Signed and sealed this 29th day of August 1972.

(SEAL) Attest:

EDWARD I LFLE'IGHElLJR. ROBERT GOTTSCHALK Atte sting Officer Commissioner of Patents 

